Production of black upon vegetable textile fibers, silk fibers, or mixtures of the same



EMILE AUGUSTE FOURNEA'UX, OF FLANGE-TESTER, ENG-LAND.

PRODUCTION OF BLACK UPQN TEXTILE "FIBER-S, SILK FIBERS, OR

MIXTURES U1 THE SAME.

No Drawing.

To all whom it may concern:

Be it'knovvn that l, EMILE AUoUs'rn FOUR- NEAUX, a subject of the King of Great Britain, residing at St. Jamess Building, Oxford street, Manchester, in the county of Lancaster, England, have invented new and useful Improvements in the Production of a l; Upon Vegetabl Textile Fibers, Sill: Fibers, or Mixtures of the Same, of which the following a specification.

As commoiny practised in calico print Works the prussiate anilin black process consists n printing or padding textile fibers or "-s with a solution containing a salt of anilin (generally the hydrochlorid, but the nitrate is also used) together with a chlorate and a ferrocyanid, generally the potassium or sodium salts. The solution may be suitably thickened and in addition to the above essential ingredients it frequently contains others, such as anilin oil, salts of the homelogues of anilin, additional catalysts such as vanadium salts, paraphenylenediamin, etc. The relative proportions of the several ingredients vary within fairly Wide limits, but the proportion of the anilin salt is nearly always in excess of the amount required for the purpose of converting the ferrocyanid into anilin hydroferrocyanid. Upon the material so prepared the black is developed by steaming, and as a rule a light chroming. The material is then washed and it may be soaped.

Resist prints are produced by printing the material with resist colors, containing alkaline and frequently also reducing agents and for colored resists suitable coloring matters, either before the black mixture is applied, or alternatively the resist colors may be printed on the prepared material, but before developing the black.

The resulting black is more or less greenable, the anilin is not Well utilized and a certain amount of tendering is unavoidable, but notwithstanding these well-known defects the process is very largely used, mainly owing to the excellence of the resist effects.

The shortcomings of the prussiate black process may be assumed to be due to the mixture becoming so acid in the course of the development of the black that the formation of ungreenable black is partly inhibited and it has been proposed to replace part of the acid used by organic acids. This can hardly be claimed to have proved a sat- Specification of Letters Patent.

' Application filed May 27,

Patented Jan. 27, 1920.

Serial No. 388,145.

isfactory solution of the problem, for while it may result in some slight improvement in resistance to greening it does not do so without causing a further and material loss of anilin.

The present invention relates to animproved process of producing prussiate anilin blacks by which these defects are very largely remedied without materially impairing the valuable features of the known process. It is based on the discovery that metaphosphoric acid, though a relatively strong acid, is yet capable of reducing the acidity of the black mixture to such an extent as not materially to interfere with the production of ungreenable anilin black.

The essential difference between my im proved process and the known process is in the composition of the solutions used, in that I replace by metaphosphate of anilin in equimolecular proportions part, usually the greater part, of the anilin salt used in excess of the proportion required to convert the ferrocyanid into anilin hydroferrocyanid.

When preparing the black mixtures or solutions the limited solubility of the metaphosphate of anilin must be considered, also the fact that concentrated solutions thereof are readily precipitated by the addition of relatively small amounts of anilin hydrochlorid, somewhat less readily by anilin nitrate. On material prepared with my solutions the black develops rather more slowly than an ordinary prussiate black, but the rate of development may be regulated on well known lines by the use of additional catalysts, as instanced by example 3.

The chemical equivalents of the metaphosphate of anilin, 2'. e. the anilin salts of orthophosphoric, pyrophosphoric, arsenic and boracic acid are capable of similar ae tion and their use comes within the scope of the invention. Of these salts, those derived from the other phosphoric acids and from arsenic acid are materially less suitable for my purpose on account of deficient solubility, the arseniate moreover on account of its toxic properties. The anilin borate, on the other hand, is unstable in aqueous solution, being extensively hydrolyzed, but boracic acid in conjunction With anilin may be used to advantage in cases Where it is desired to reduce the acidity further than can be done conveniently by means of theby Way oi illustration and not necessarily as limitations as the proportions may be varied or modified as found advantageous or desirable.

Examples.

Example l.To five hundred and sixty c. c. prussiate chlorate standard add the solution of ninety-seven and one half grains anilin-hydrochlorid in two hundred and eighty-five c. c. Water and two 0. c. anilin oil, then twenty-five c. c. chlorate solution and four hundred and, sixty c. c. phosphoric standard. Bulk to one thousand four hundred c. c.

Etc-ample 2.To five hundred and twenty c. c. prussiate chlorate standard addone hundred c. c. paste and the solution or one hundred and five grams anilin-hydrochlorid in one hundred and eighty-live c. 0. Water, then eighty-five c. 0. acid metaborate solution, twenty-five c. c. chlorate solution and three hundred and eighty c. c. phosphoric standard. Bulk to one thousand three hundred and fifty c. c.

Example 3.To six hundred c. c. prussiate chlorate standard add two hundred and twenty-five c. c. paste and the solution of one hundred and thirty grams anilinhydrochlorid in tWo hundred and sixty-five c. 0. Water, then one hundred and sixty c. c. acid inetaborate solution, twenty c. c. chlorate solution, five and one half grams paraphenylenediamin-dihydrochlorid dis solved in sixty c. 0. Water and 5 c. c. of a solution of vanadium chlorid of such con centration as to correspond to one gram commercial ammonium vanadate in tWo hundred c. 0. Bulk to one thousand four hundred c. 0.

Example 4.To five hundred and eightyfive grams prussiate black standard add three hundred and thirty grams paste, ten c. c. anilin oil, eight grams metaphosphoric acid dissolved in sixteen c. c. Water, then add thirty-two and one half grams anilinhydrochlorid, one hundred c. c. acid metaborate solution and twenty-two and one half 0. c. chlorate solution. Bull: to one thousand one hundred grams.

The several standards mentioned in the above examples are prepared as follows:

Phosphoric standarcl.'lo one thousand seven hundred c. c. paste add eighty grams metaphosphoric acid dissolved in one hundred and sixty c. 0. Water, then slowly, While stirring ninety-three c. c. anilin. Bull; to two thousand c, c.

Pi'ueaz'ute ,tlome standard-Dissolve "116 hundred anc tw E grains ferrocyanit of edit in live hundred c. c. boiling Water, cool, and add one hundred and sixty-six c. c. chlorate solution and Water to bulk to e'i 1" hundred c. c.

1 meet l lac/ a stamZmxZ.-Dissolve one red and twenty grams ferrocyanid 01" lot, in five hundred c. c. paste and t r c. Water, then add eighty grams chlorate of soda and finally, when cool, add one hundred and thirty anilinhydrochlcrit. Bulk to e hundred c. c.

flitiorctc s0Zut-c;2 .Dissolve one hundred and ms cnlorate of soda in Water to bulk t two hundred and trrei y c. c.

A 05c mambo rate solution. l)issolve thirt"- grains bora and twenty-five grams 1016 acid in Water to bulk to two hundred Preferably a neutral starch gum 'on thickening.

Xtures given in examples, 1 intended for padding purposes,

3 are in nainpie 1- printing purposes.

i pplication and after-treatment ma be as in the ordinar russiate black -orc-ces w, n J 1 t 1 claim as my invention and desire Wna to secure by Letters Patent is:

1. An improved process for the production of prussiate anilin black upon vegetable textile fibers, silk fibers, or mixtures thereof characterized by the use of meta- EMILE AUGUSTE FOURNEAUX.

Witnesses S. l/V. GILLETT,

HERBERT ROWLAND ABBEY. 

